Indigoid dyestuff



Patented Dec. 5, 1933 PATENT oFFicE INDIGGID DYESTUFF Norbert Steiger, Franlrfort-on-the-Main, and Walter Brenner, Frankfcr on the Main Fechenheim, Germany, assignors to General Aniline Works, line, New York, N. Y., a corporation of Delaware No Drawing. Application January 6, 1933, Serial No. (556,579, and in Germany January 11, 1932 5 (Claims.

(wherein two X mean methyl, the third X an alkoXy-group, the fourth X hydrogen or halogen, Y means S or NH and R a radical of a hydroXy-thionaphthene or an-isatine of the henzene or naphthalene series which may contain as substituents alkyl, alk xy or halogen).

The either component or" these dyestuffs (left in the above formula) belongs in any case to the group of indigoid dyestufi components described in our U. S. applications Ser. No. 650,578, relating to "HydroXy-thionaphthene compounds (throughout the specification numbered for the sake of brevity I) and Ser. No. 650,580, relating to Isatine compounds (throughout the specification numbered for the sake of brevity II), both filed on the'same date. I

The process of making symmetrical dyestuffs of this kind is by oxidizing the hydroXy-thionaphthenes of our U. S. application Ser. No. 650578 (I). Asymmetrical dyestuffs are obtained by condensing the same hydroxy-thionaphthenes with an isatine or a reactive oz-dE- rivative of this isatine or of a 2.3diketo-dihydrothionaphthene, these components being of the benzene or naphthalene series. Furthermore such dyestuiis are produced by condensing an isatine of our U. S. application Ser. No. 650,580 (II) or a reactive lac-derivative thereof or a 2 derivative of. the 2.3-diketo-dihydro thicnaphthene corresponding to the hydroxy-thionaphthenes described in our U. S. application Ser.No.650,578 (I) with a hydroXy-thionaphthene of the benzene or naphthalene series.

Dyestuiis containing halogen may be prepared either by starting from halogen-containing materials or by an after-halogenation of the dyestuffs if the either of their components is still capable of being halogenized.

The dyestuiis thus prepared show different shades according to the position of the substituents and according to the second indigoid dyestuff component used. They are partially distinguished by a remarkable iastness.

Amongthe dyestuffs containing an isatineof our application II those of the benzene series representing the type Z-hydroxy-thionaphthene- 2'-indol-indigo are of a particular importance. They dye violet to blue shades of a very good fastness to boiling together with an excellent fastness to water-dropping.

Whereas the known dyestuffs of the violet-series dont meet all requirements of practice (since those from halogenated isatines and hydroxythionaphthenes dont possess a'fastness to boiling sufficient to all purposes and since the dyestufis. of the iso-dibenzanthrone series possess a good fastness to boiling but only a moderate fastness to water-dropping), by the violet dyestuffs obtained according to the present invention the dyestuff-assortment hitherto known is remarkably completed.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees; but it is, however, to be understood that our invention is not limited to. the \particular products nor reacting conditions mentioned therein.

Example 1 10 parts of 6.7-dimethy1-5-methoXy-3hydroXy-thionaphthene, described in Example 1 of our application I, are dissolved at 50 in 200 good fixation in printing. It corresponds to the following formula:

The symmetrical dyestuff which may be obtained in the same manner from the 1.2.4-xylidine5-sulfonic acid after transforming it into the 4.5-dimethyl-7-methoxy-hydroXy-thionaph thene, dyes cotton from the vat greenish blue shades.

H300- 43g coocH3 0:0 CHs- S S- CH3 I CH3 CH2 Example 2 parts of the 6.7-dimethyl-5-methoxyhydroxy-thionaphthene, 6.6 parts of 2.1-naphthoxy-thiophene-anil and 120 parts of glacial acetic acid are heated while stirring to 115 during 5 hours. The separated dyestuff is filtered off by suction, dried and made to a paste by means of sulfuric acid. The product thus obolotained dyes the fiber from a golden-yellow vat olive shades and corresponds to the following formula:

HaCO- OO The dyeings are distinguished by an excellent fastness to light. The dyestuff may also be used for cloth-printing.

l5 HaC Example 4 46 parts of the 4.6-dimethyl-7-ethoxy-hydroXy-thionaphthene are dissolved at 80 in 500 parts of chlorobenzene and condensed at 85 with a solution of 4-methyl-5chloro-7-methoxyisatine-a-chloride, prepared at 100 from parts of l-rnethyl-5-chloro'l-methoxy-isatine, 52 parts of phosphorus pentachloride and 500 parts of chloro-benzene. The dyestuif forms a greenish yellow vat and dyes and prints cotton bright greenish blue shades of good fastness qualities. It corresponds to the following formula:

OCHa

Example 5 45 parts of the 4.7-dimethyl-6-ethoxy-3-hydroXy-thionaphthene, described in Example 3 of our application I, are heated for some time with 55 parts of 2.3diketo-dihydro-thionaphthene-2- (p-dimethyl-amino -anil in 100 parts of glacial acetic acid. The scarlet dyestuff thus obtained corresponds to the following formula:

0:0 HaCzO -S/ S C lHa It dissolves in concentrated sulfuric acid with a black-violet color, forms a yellow vat and dyes cotton bright scarlet shades of good fastness. The dyestuff may also be used for cloth-printing.

Example 6 By oxidizing the sodium salt of the 4.5-dimethyl-6-methoxy-3-hydroXy-thionaphthene- 2 carboxylic acid, described in Example 4 of our application I, in an alkaline solution with e. g. ferric potassium cyanide, the symmetrical dyestuff corresponding to the following formula:

is obtained; it has an orange color and dissolves in sulfuric acid with a bluish violet tint.

Example 7 H30 0 0 CH3 21 parts of the 4.5-dimethyl-6-methoxy-3-hydroxy-thionaphthene, described in Example 4 of our application I, are heated in 50 parts of glacial acetic acid with 32 parts of 6-methoxy-2.3- diketo-dihydro thionaphthene-Z (p-dirnethylamino) -anil. The dyestufi thus obtained corresponds to the following formula:

HaC- CO OO o=0 H300 s s OOH:

It dyes cotton from a yellow vat yellowish orange shades of remarkably good fastness to boiling and dissolves in concentrated sulfuric acid with a violet-blue color.

Example 8 4.6-dimethyl 5-chloro-7-1nethoXy-3-hydroxythionaphthene, described in Example 5 of our application I, is oxidized for instance according to Example 6. In this manner a reddish violet symmetrical thioindigo-dyestuff corresponding to the following formula:

01- c 0 c o 01 1130 s s 0 H3 1 0 CH3 0 CH3 is obtained.

Example 9 35 parts of 4.5-benzo-23-diketo-dihydro-thionaphthene-2-(p-dimethyl-amino) -anil are heated to 100 for 4 hours with 24 parts of LG-dimethyl -5- chloro -'lmethoxy 3- hydroxy-thionaphthalene and 50 parts of glacial acetic acid.

In this manner a dyestufi is obtained which cor responds to the following formula:

and which dyes cotton from an orange vat claret shades of good fastness qualities especially to light.

Example 10 The droyXy-thionaphthene, described in Example 6 of our application I, is dissolved in spirit of 30% strength with 1 molecule of caustic soda solution and oxidized with ferric potassium cyanide. The symmetrical thioindigo-dyestuff thus obtained corresponds to the following formula:

and dissolves in concentrated sulfuric acid with an olive-green color, dyeing cotton from a yellow vat bright reddish violet shades of good fastness.

The same symmetrical thioindigo-dyestuff may also be obtained by adding 1 part of the 1.4- dimethyl -2- chloro -3- methoxy-benzene-5-thioglycollic acid, described in Example 6 of the above said application) to 5-10 parts of chloro-sulfonic acid and precipitating by means of ice-water after some hours standing at 10-20.

Example 11 The symmetrical thioindigo obtained from the 4.7-dimethyl-5-methoxy- 6- chl0ro 3 hydroxythionaphthene, described in Example 7 of our ap plication I, has a reddish violet color and dissolves in concentrated sulfuric acid with a green tint.

By combining this hydroxy-thionaphthene with Z-anils of 2.3-diketo-dihydro-thionaphthenes or isatines dyestufis of bright shades and good fastness qualities are obtained. The following table shows the properties of some dyestuffs obtained in this manner:

allege of C 1 f collor of the e ye- 0 or 0 so n 1011 in Combmed Wlth ing on the vet concentrated cotton sulfuric acid 2.3 diketo dihydro thio- Bluish Yellow Yellowish green naphthene-Z-anil. red. 4 methyl 6 chloro 2.3 Bluish Yellow Green.

diketo dihydro thionaphred. thene-Z-anil. 6 methoxy 2.3 diketo Scarlet. Yellow Yellowish green dihydro thionaphthene 2-anil. 5.7 diehloro isatine a Vi0let- Golden- Bluish green.

chloride. yellow. 4 methyl 5 chloro 7- Blue Greenish Green.

methoxy isatine a yellow. chloride.

Example 12 4 5-dimethyl-6-chloro-7-methoxy-3-hydroxythionaphthene of 132-133 melting point yields a 4.7-dimethyl-5-ch1oro-6-methoxy-3 -hy symmetrical thioindigo which corresponds to the. following formula:

CH3 CH3- dyeing cotton reddish violet shades of a. very good fastness to boiling and to chlorine.

The dyestuff obtained by combining the same hydroxy-thionaphthene with 4-methyl-6-ch1oro- 2.3-diketodihydrothionaphthene 2 anil dyes cotton pink shades.

Example 13 CH3 CH3 and dissolves in concentratedsulfuric acid with a green color and dyes from a'yellow vat bluish red shades.

Example 14 29 parts of 4.7-dimethyl-5-methoxy-6-bromohydroxythionaphthene are dissolved in 300 parts of chloro-benzene and condensed with an isatinea-chloride-solution, prepared from 25 parts of 4.6-dimethyl-5.7-dichloro-isatine, 22 parts of phosphorus pentachloride and 300 parts of chloro -benzene by heating to 95100. In this manner a dyestuif is obtained, corresponding to the following formula:

dyeing cotton from a yellow vat bright violet shades and dissolving in concentrated sulfuric acid with a green color.

Example 15 4 chloro-5-methoxy-6.7-dimethyl-3-hydroxythionaphthene, described in Example 9 of our application I, is condensed with 4-methyl-6-chlor0 2.3 diketo-dihydro-thionaphthene-2-(p-di methyl-amino)-anil. In this manner a dyestufi is obtained which corresponds to the following formula:

C1 CH3 It dissolves in concentrated sulfuric acid with an olive-green color and dyes cotton from a yellow vat ruby-red shades of good fastness.

Example 16 23.9 parts of 5-ch1oro-l.6-dimethyl-7-methoxyisatine, described in Example 1 of our application II, are heated in chloro-benzene with 21 parts of phosphorus pentachloride. The ca-(JhlO- ride thus obtained is condensed with 21.3 parts of 4.7 dimethyl-5-chloro-3-hydroxy-thionaphthene. In this manner a dyestuff is obtained, corresponding to the following formula:

on CH3 dyeing cotton from a yellow vat reddish blue shades of an excellent fastness to boiling and chlorine. The solution of this dyestuff in con- Icentrated sulfuric acid has a blue-green tint.

When starting, instead of from the methylated, from the ethylated isatine and working in an analogous manner, the corresponding ethoxycompound is obtained which is very similar as to its properties to the foregoing described methoxycompound.

Example 17 24 parts of 6-cholro-4J7-diniethyl-5-1nethoxyisatine, described in Example 2 of our application II, are transformed into the matinee-chloride by heating with 21 parts of phosphorus pentachloride in a solution of chloro--bcnzena The a-chloride is condensed with 25 parts of 5. 6. '7-

trich1oro-3-hydroxy-thionaphthene. The dyestuff thus obtained corresponding to the following formula:

dissolves in concentrated sulfuric acid with a green color and dyes cotton from an orange vat bluish violet shades of good fastness to waterdropping.

Ezrample 18 By condensing 5-methoxy-6.7-dimethyl-isatine, described in Example 3 of our application II, with 2.1-naphthoxy-thiophene an indirubine of an olive-brown color is obtained which corresponds to the following formula:

is obtained.

By condensation of the ca-ChlOlidB of the 5- methoxy-6.7-dimethyl-isatine with 5. 6. 'l-trichloro-hydroXy-thionaphthene a violet dyestuff is obtained.

Example 19 2'? parts of 7-bromo-4.6-dimethyl-5-methoxyisatine, described in Example 4 of our application II, 25 parts of phosphorus pentachloride and 200 parts of chloro-benzene are stirred at 100 for about 2 hours until the formation of a clear solution. The solution of the isatine-u-chloride is condensed at with a solution of 23 parts of 4.?-dimethyl-5-chloro-3-hydroXy-thionaphthene in 480 parts of chloro-benzene. The dyestuff thus produced corresponds to the following formula:

CH3 CH3 Example 20 By starting in the fore oing example from the corresponding chloro usstituted isatine and by condensation with, 5.6.7-trichloro3-hydroxythionaphthene a bright violet dyestuff of good fastness to boiling and to light is obtained; it corresponds to the following formula:

H30 0- -O O O 0- O1 lIaC- NH S- Cl I Cl C1 The wderivative of the unhalogenated 4.6-dimethyl-5-methoxy-isatine yields e. g. with 4.7- dimethyl-5-chloro-B-hydroxy-thionaphthene a violet dyestufr of very good fastness.

l.7-dimethyl-5-chloro-6-'nethoxy-isatine yields with 5.6.Z-trichloro-3-hydroxy-thionaphthene a violet dyestuii.

We claim:

1. The indigoid dyestuffs corresponding to the general formula (wherein two X mean methyl, the third X an alkoxy-group, the fourth X hydrogen or halogen, Y means S or NH and R a radical of a hydroXy-thionaphthene or an isatine of the benzene or naphthalene series which may contain as substituents alkyl, alkoxy orhalog'en), which dyestuffs dye cotton from the vat various shades.

2. The indigoid dyestuffs corresponding to the general formula CH3 CH3 which dyestufi dyes cotton from the vat gray shades of a good fastness.

or o o o 0- c1 o=o 11300- s s- OCH2,

CH3 H3 which dyestufi dyes cotton from the vat reddish 4 The indigoid dyestufi corresponding to the formula OH: I

violet shades of a good fastness.

5. The indigoid dyestufi corresponding to the formula nio0 oo o 0- c1 o=o 1130- NH s 01 which dyestuff dyes cotton from the vat violet shades of a good fastness.

- NORBERT STEIGER. WALTER BRUNNER. 

